Metalliferous substantive dyestuffs



Patented Aug. 31, 1943 DIETAILIFEROUS SUBSTANTIVE l DYESTUFFS GeorgesKopp, Paris, France;' vested in the Alien Property Custodian No Drawing.Application March 6, 1940, Serial N0. 322,623. In Great Britain'March28, 1939 6 Claims.

The direct dyeing of natural or regenerated cellulosic fibres in shadesfast to light hasrecently made great progress by the introduction ofsubstantive metal azo complexes. Such products have been obtained bymetallisation of substantive azo dyestuffs derived from diphenyl basesof the type 4:4'-diamino diphenyl. It is known that certain amongstthese polyazo dyestuffs, dye cotton directly in yellowish brown shadesfast to washing andlight. Their' constitution approaches in general thefollowing scheme:

X being a coupling .component carrying an ortho hydroxy carboxylicgrouping, Y being a sulphonated monoazo dyestuff capable of couplingwith the intermediate body and capable of forming complexes withpolyvalent metals, and D being an azotized diphenyl base of the type ofbenzidine. either diazotized or tetrazotized.

The dyestuffs of this type dy cotton yellowish brown and it had not beenhitherto found possible to obtain purple browns without injury beingdone to the essential dyeing properties.

It has been found that purple browns of great interest are obtained bychoosing as Y component, a compound of the following type HO HO I -N=NII l, i the radical It being substituted by a nitro group, and one ofthe radicals I and II carrying-an 50:11 group.

Certain of the dyestufis of this constitution dye cellulosic fibres,such as cotton or viscose, purple brown. When the nitro group occurs inthe 0 position, relative .to the OH group, the resistance to light issharply increased relative to the correponding dyestufis deprived ofthis substituent.

The metalllsation of thes dyestuffs can. be done under variousconditions of reaction medium, temperature, duration and pressure. Themetallising agents taking part in this reaction can be finely dividedmetals, oxides, hydrox- The base may be tallic oxide complexes, such asammdniacal cupric oxide or Fehllngs solution.

The invention is illustrated in the following examples:

x Example 1 There is prepared according to the usual method, anintermediate body with the help of 184 parts of benzidine and 140 partsof salicylic acid.

- Into this intermediate body there is run rapidly the monoazo dyestuffprepared by coupling in presence of sodium carbonate the diazo compoundof 6 nitro-2-aminophenol-4-sulphonic acid (234 parts) with 110 parts ofresorcinol. Stir at low temperature until the first compound(benzidinesalicylic acid) has completely disappeared.

A solution of 300-parts of crystallised copper su1-' phate is added andthe mixture heated to C. for onehour. 5

The dyestufl is isolated by filtration and dried. This dyestufl dyescotton in a, bath of sodium carbonate purplebrown shades very fast tolight. Its excellent afilnity for cellulosic fibre allows of obtainingthe dark' brown colours termed "nesros head.

The non-nitrated dyestufl, already previously described, gives brownswhich are too yellowish.

Its tinting with the help of blue black or violet colours gives shadesapproximating those of the new dyestufl of this example, withouthowever,

attaining its brightness and its excellent fastness to light, nor itsgood yield.

The above dyestufl can be equally well isolated before the'treatmentwith sulphate of copper, the latter can be incorporated after drying thedyestufl, or fixed by a subsequent treatment of the dyeings. Theproperties of the dyeing will vary according to the quantity of coppersulphate used.

Example 2 There is prepared accordin to the usual technique a diazotizedintermediate body, starting dimethyl-diphenyl) and 152 parts oiE-methyl-L hydroxy benzoic acid.

There is prepared on the other hand, a monoazo dyestuif starting with234 parts oi fi-nitro- -Z-amiho phenol-4-snlphonic acid and lid partsor? resorcinol. This dyestufi is isolated by salt ing out. The dyestufipaste i diluted in 3000 parts of water and 1509 parts of flit???ammonia, the suspension is boiled and a solution of 350 parts ofcrystallised copper sulphate in 2000 parts i ides, salts oi inorganic ororganic acids or meas of warm water added. Thecupriterous dyestufi isisolated by salting out and filtration. diluted in 5000 parts of coldwater.

The suspension of cuprlferous dyestufi is al- It is lowed to flow into asuspension of the above intermediate product, and the whole stirreduntil the intermediate body disappears. It is heated to 50 C., theexcess of alkali neutrallsed loy acetic acid, and the dyestuif isolatedby addition of salt, filtration and drying. The dry product is groundwith suitable quantities of carbonate of soda and if desired,pyrophosphate oi soda.

The dyestufi thus obtained dyes cotton very v purple brown, and is veryresistant to light and to Washing. its great resistance to light rendersit particularly interesting for obtaining fashionable and very brighttones on hosiery thread.

The resistance to light is still further improved when the dyeings aremade in an excess of sulphate or other salt of copper added to the dyebath, for example after the exhaustion of the dye.

Example 3 The salicylic acid in Example 2 is replaced by an equivalentquantity of ortho-cresotinic acid. The intermediate compound thusobtained is coupled with the metalliferous complex resulting from theaction oi 100 parts of copper sulphate,

' 160 parts oi nickel sulphate, and fill parts of cobalt nitrate on themonoazo dvestufi obtained by coupling the dlazo compound of 234 parts of6-nitro-=2=arnlno=phenol=4l=sulphonic acid with ill) parts ofresorcinol.

The dyestufi isolated in the usual manner dyes vegetable fihres violetlorotvn shades, very fast to light. The shades and. properties of thenew dyestuffs he modified by replacing the copper salts (on the "wholeor partly) with salts of other polyvalent etals or with a of these saltsfixed on the dyestu in nature or on the iibre.

I declare that I claim is:

1. Process for making purplish lorctvn dyestuffs which consists inInetalllslng dyestuffs of the gen eral formula where D is a dlsazotizeddiphenyl base oi the bennidine type, as is a coupling component having acarlooxylic group ortho to ahydrors =group and being a member of thebenzene series, and Y is the dye-stud component of the general iormule:

the diphenyl base being coupled at the resorcinol group of said Ycomponent. i

2. Process of making purplish brown dyestuiis oi the type as set forthin claim l. which consists in tetrazotising the dlphenyl base D andcoupling with the components X and Y.

3. Process for obtaining purplish brown shades on N02 mes es whichconsists in metallislng on the fibre dyestuffs of the general formula YWhere D is a disazotized diphenyl base of the benzldine type, K is acoupling component having a carboxylic group ortho to a hydroXy-groupand being a member of the benzene series, and Y is the dyestuficomponent of the general formula:

OH on N02 sons the diphenyl lease being coupled at the resorcinol groupof said Y component.

l. Process for making purplish brown dyestuffs which comprisesdiazotising a diphenyl base of the henzidine type, coupling with acoupling component having a carboxylic group ortho to a hydroxy-groupand being a member of the hen-= zene series, and diazotising the productand coupling same with the metallised dyestuii component of the generalformula:

OH OH N0 the diphenyl lease heing coupled at the resorclnol group ofsaid component.

5. Process of making purplish brown dyestufis which comprisesnietallising with a plurality of salts of difierent metals dyestuffs ofthe general formula where D is a disazotized diphenyl lease of thehenzidine type, is an aromatic coupling component having a carlooxylicgroup ortho to a hydrozy -group and being a member of the benzeneseries, and Si" is a dyestulicomponent of the gen-= eral formula:

